Process for the treatment of abietyl compounds and products produced thereby



Patented 24,

mocass roam 'raaarmr or ABIETYL COMPOUNDS AND PRODUCTS PBODUCED r EdwinlLIittmann.

Wilmington, Del. inimito Hercules Powder Oompany, Wilmington, Del,

a corporation or Delawarev No Drawing. ormnsi application June 12, 1936,

Serial No..84,8"l7. Divided and this application Y September 9, 1936, Serial N0. 100,041

12 Claims. (CL 260-666) This invention relates to a process for the treatment of rosin, rosin acids, and compounds derived from rosin. which contain the hydrocarbon nucleus characteristic of rosin acids, and to the products thereof. More specifically, this invention relates to the treatment of such compounds, so as to decrease their unsaturated char-.

- acteristics, and to the products resulting from such treatment.

This treatment in accordance with this invention comprises essentially contacting rosin, a rosin acid, .or other compound containing the hydrocarbon nucleus of a rosin acid with a catalyst of the type hereinafter described, in a manner to exclude the possibility of reaction between Y the rosin or rosinderivative and any added material capable of reducing the unsaturation of the rosin acid nucleus. As a result of such treatment a change in the chemical and physical properties of the rosin or rosin derivative takes place, and the resultant product will. be found to have a greatly decreased unsaturation. In many cases, the product will also be found to have a higher melting point and improved properties. These changes in the physical and chemical characteristics of the material are believed to be due to an intraand inter-molecular rearrangement of the hydrogen .atoms therein, with no change. in the carbon skeleton.

The catalysts which may be used in eiiecting this change are those which catalyze the hydrogenation of unsaturated organic compounds, as, for example, nickel, copper chromite, platinum, palladium, etc. While both base and noble metal hydrogenation catalysts are useful in producing this change or intraand inter-molecular rear- 7 rangement, a of a noble metal supported on .an inert carrier is particularly eiiectlve. Palladium-in an amount within the range of about 1% to'ahout 25% supported on an inert carrier, such as, for example, granular alumina or fibrous asbestos, is preferred. v

A novel type 01'- palladium catalyst, devised especially for the process in accordance'with this invention, may be made as follows:

A solution containing 1 part by weight of palladium chloride, 2 parts by weight of concentrated hydrochloric acid and 8 parts by weight of water isadsorbed on 15 parts by weight or granular la alumina. This mixture is then treated with .2

parts by weight or an approximately 37% femaldehyde solution, followed with approximately 15 parts by weight of an approximately 10% sodium hydroxide solution, enough to make the solution slightly alkaline and precipitate the palladium black. After thorough agitation, the mixture is filtered, washed with water, dilute acetic acid,fandthen again with water, until neutral. The product is then finally dried in an oven at 80 C. to 100 C. This catalyst is most eflicient in the treatment in accordance with this invention and its use is preferred.

Rosin is a mixture of isomeric rosin acids having the formula ,CmHzeCOOH, in which the group CmHza has beenv shown to contain two double bonds and to possess an alkylated phenanthrene nucleus. It will be understood that when refer-- ence is made herein to arosin acid, a carboxylic acid found in rosin and containing the group CuHzo, is meant. More than fifty diiferent isomeric rosin acids have been reported in the literature. The best known of these acids are abietic acid, sapinic acid and d-pimaric acid. The relative proportions in which these and the other isomeric rosin acids occur in a given sample of rosin depends on the source of the rosin. Thus,

7 wood rosin contains more abietic acid than any of the other acids, while American gum rosin contains more sapinic acid. French gum rosin contains more d-pimaric acid.

-meric acids is capable of reaction in accordance with this invention, and for the purposes of this invention they are entirely equivalent. Thus, for example, any of the various grades of American wood rosin,' American gum rosin, French gum rosin, Portuguese gum rosin, Spanish gum rosin etc., may be treated to'reducetheir unsaturated characteristic. The several isomeric acids found in various types of rosin, for example, abietic acid, d-pimarlc acid, sapinic acid, etc., may be separated and treated in purified form if desired. Likewise, compounds derived from rosin or the rosin acids without alteration of the CuHa nucleus are. equivalent-to the rosin or rosin acids for the purposes of this invention. Further, partially hydrogenated rosins and compounds containing a partially hydrogenated hydrocarbon nucleus of a rosin acid are still further reduced in unsaturation when treated by theproces in accordance with this invention and are likewise equivalent to the tmhydrogenated compounds from the standpoint of this invention. Such compounds are characterized by containing somewhere in their structure the hydrocarbon group CnHai containing one double bond, and

The class of compounds which may be treated in accordance with the process of'this invention todecrease their unsaturation and improve their properties are characterized by containing somewhere in their structure an alkylated phenanthrene group'containing two double bonds and,

having the formulaCmHzqora partiallyhydrogenated phenanthrene group containing one .double bond and having the formula CmHai. No generic term has developed in the literature to cover this closely related group of compounds, so for convenience I will term them Rosinyl compounds".

The term Rosinyl compound will hereinafter be process which materially alters the hydrocarbon skeleton of the rosin acid.

In addition to the various rosins, rosin acids,

partially hydrogenated rosins, and partially hy-.

drogenated rosin acids mentioned hereinbefore,

there are many other fRosinyl compounds which may be treated in accordance with this invention.

Thus, for example, I may treat the monohydric and polyhydric alcohol ,esters of rosins, rosin acids, partially hydrogenated rosins, or partially hydrogenated rosin acids, such as, for example, their esters with methanol, ethanol, propanol, isopropanol, butanol, iso-butanol, ,oleyl alcohol, lauryl alcohol, abietyl alcohol, hydroabietyl alcohol, furfuryl alcohol, tetra-hydroiurfuryl alcohol, ethylene glycol, diethylene glycol, triethyle'ne glycol,. glycerol, erythritol, pentaerythritol, surbitol, mannitol, mixturesthereof, phenol, etc. I may treat alcohols produced from rosins and rosinacids, partially hydrogenated rosins, or partially hydrogenated rosin acids, by'the reduction -of the carboxyl groups of the rosin acids, such as,

for example,'abietyl alcohol, dihydroabietyl alcohol, sapinyl alcohol, dihydrosapinyl alcohol,

methyl ether, pimaryl ethyl ether, pimaryl propyl pimaryl alcohol, dihydropimaryl alcohol, etc.

Again, I may treat ethers formed by the etheriflcation of the alcohols derived from rosins, rosin acids, partially hydrogenated rosins, and partially hydrogenated rosins acids with aliphatic, aromatic, or hydroaromatic alcohols, such as, for example, abietyl methyl ether, abietyl ethyl ether. abietyl butyl ether, abietyl phenyl ether, abietyl bornyl ether, abietyl terpinyl ether, primaryl ether, pimaryl phenyl ether, pimaryl bornyl ether,

.-pimaryl terpinyl ether, sapinyl methyl ether,

sapinyl ethyl ether, sapinyl propyl-ether, sapinyl 'butyl ether, sapinyl phenyl ether, sapinyl bornyl ether, sapinyl terpinyi ether, etc. Likewise, I

may treat produced by the doomboxylation or rosins, rosin acids, partially hydro- 'genated. rosins, partially hydrogenated rosins acids, etc., such as, for example, those produced by the treatment ofrosins, 'rosin acids, partially hydrogenated rosins and partially hydrogenated rosin acids with a catalyst, as, p-toluen'e sulphonic acid, at an elevatedtemperature, according to the prom disclosedfin United States Patent 1,975,.-

- 211, to Alan C. Johnston, or by treatment with fullers earth atan elevatedtemperature.

Compotmds which contain in their structure a rosinacidnucleusorpartiallyhydrogenatedroein.

acid nucleus which has undergone the intraand inter-molecular rearrangement produced by the process in accordance with this invention, will hereinafter be referred to as Hyex compounds. The catalytic reaction by which the unsaturation of the rosin acid nucleus or the partially hydrogehatedaosin acidnucleus is reduced will be termed the Hyex reaction."

In carrying out the process in accordance with this invention, the Rosinyl compound will be brought into contact with a hydrogenation catalyst, preferably at an elevated temperature in order that apractical reaction rate may be obtained; however, the use of an elevated temperature is not necessary for the accomplishment of the desired result. The optimum temperature range for most satisfactory results is from about C. to about 250 C.,and a temperature of about 220 C. to about 250 C. is preferred. Pressure has little or no efiect on the reaction, which may be carried out in vacuo or at superatmospheric pressure if desired. Since atmospheric pressure is most convenient from an apparatus standpoint, such will usually be used.

a As thorough contact between catalyst and rosin or rosin acid can best be obtained when the.

Rosinyl compound or partially hydrogenated Rosiny compoundis in liquid or vapor phase, the Rosiny compound or partially hydrogenated. ,Rosiny compound will preferably be heated to render it sufliciently fluid for desired contact with the catalyst. While, under certain cir-' cumstances it is desirable to carry out the reaction in the vapor phase, ordinarily I prefer to carry it out with a liquid phase. The Rosinyl compound or tine partially hydrogenated Rosin-- yl compound may be in the molten condition or may, if desired, be dissolved in a suitable inert,

non-reactive solvent, and the solution-sh formed treated with a hydrogenation catalyst. "Any solvent for the compound treated which is not a poison to a hydrogenation catalyst and which does not contain catalyst poisons as impurities and which does not enter into the Hyex reaction is suitable for this purpose. Thus, for example, aliphatic hydrocarbons, the various petroleum fractions, monocyclic aromatic hydrocarbons, hy-

- drogenated aromatic hydrocarbons, etc., are suitable for the purpose. The aliphatic hydrocarbons and the various petroleum fractions are particularly useful.

In accordance with this invention it is essential that the treatment of the Rosinylf compound be carried out in such'a manner that no reaction can occur between the compound being treated and any added material capable of reducing its unsaturation under-the conditions of reaction. In

other words, any material which, under the conditions of treatment, will react with the Rosiny compound to reduce its unsaturation must be excluded. No added hydrogen is present during the treatment. However, inert substances and substances capable of reaction with the compound which do not reduce its \msaturation, may be present. Thus, inert solvents, inert gases,

may be present. While the treatment may be carried out in theprcsence of air, it is preferable to treat the Rosinyl! compolmd or the partially hydrogenated "Rosinyr' compound inan atmosphere of a more inert gas, as, for example, carbon dioxide, nitrogen, etc. f

Y The treatment in accordance with this invention may be carried out simultaneously with other reactions, which do not involve a change in the 'imsaturated characteristic ofthercslnnuclem.

' Thusfrosin or a rosin acid may be treated 'tivity of the catalyst employed. Upon the completion of the treatment, the resultant product may be easily separated from the catalyst by filtration. The product secured after the removal of the catalyst, if volatile, may if desired, be distilled under reduced pressure and separated into two or more fractions. Where a high melting point product is desired, such maybe secured by the removal of the low-boiling fraction from the catalytically-treated material.

The product, in accordance with this invention, may be produced by one or more of the three alternate embodiments of the method in accordance with this invention. By the first of these alternate'embodiments the corresponding Rosinyl compound may be treated, either alone or in solution, with a suitable catalyst to produce the Hyex reaction, as-described hereinbefore. This embodiment will be most advantageous for the treatment of rosincompounds which are free from impurities which will poison the catalyst, or which are not of such nature that they act as catalyst poisons. Thus, rosin may be contacted with a catalyst to produce a Hyex rosin, or a rosin ester may be passed over a catalyst to pro-- duce a Hyex rosin ester.

' By a second embodiment of the method in accordance with this invention a Rosinyl compound may be treated with a suitable catalyst to produce the Hyex reaction, and simultaneously reacted, either alone or in the presence of a solvent, with some other material which is incapable of affecting the unsaturation of the rosin acid -or partially hydrogenated rosin acid nucleusor of poisoning the hydrogenation catalyst. Thus, a mixture of wood rosin and methanol may be treated with a suitable catalyst at an elevated temperature and pressure to produce a Hyex methyl abietate, which is identical in properties with the product secured'by subjecting methyl abietate to the Hyex reaction.

By a third embodiment of .the method in accordance with this invention a Rosinyl compound may be treated, either alone or in solution, with a suitable catalyst to produce the Hyex reaction and the productso formed reacted with another material to produce the desired product. .Thus,.for'example, any of the difierent rosins may be contacted with a suitable catalyst, as

- hereinbefore described, to produce a Hyex rosin. and then esterifled by reaction with an alcohol to produce the'Hyex-rosin ester. and the Hyex rosin ester so produced will be identical in properties with the Hyex rosin ester produced according to the first or second embodiments of my invention.

A wide variety of Hyex compounds may be prepared by this embodiment of my invention. Thus, any one of the rosins, rosin acids, or partially hydrogenated rosins mentioned above may be subjected to the ,Hyex reaction, and then decarboxylated as, for example, by heating in contact with fullers earth or a sulphonic acid cat- 1 al'yst to produce a Hyex rosin oil. A rosin or rosin ester may be subjected to Hyex treatment and then reduced to the corresponding alcohol,

etherlfled with another alcohol, such as, for example, one of the aliphatic, aromatic, or hydroaromatic alcohols mentioned hereinbefore. Al-

ternately, 'a rosin acidmay be reduced to the corresponding alcohol, as for example, by catalytic treatment with hydrogen'and the product subjected to the Hyex reaction and then etherified.

This third embodiment-of my invention is particularly useful for the production of Hyex compounds, which cannot be easily produced by the first or second alternative methods, due to the corresponding Rosinyl compound or partially hydrogenated RosinyPcompound being of a nature such that it acts as a poison to the catalyst in the Hyex reaction. Thus, for example, many of the metallic salts of rosin acids, or partially hydrogenated rosin acids have a tend- --ency to poison the catalyst or to contain catalyst poisons unless proper precautionary measures are taken and, hence, cause difliculty in the Hyex reaction. Hyex rosin salts, however, may be readily prepared by subjecting a rosin acid or a partially hydrogenated rosin acid to the Hyex reaction and then forming the salt of the Hyex rosin acid produced. Thus, any one of the rosins, rosin acids, or partially hydrogenated rosins mentioned above may be subjected to the Hyex reaction and-then reacted with a metallic hydroxide or other metallic compound, capable of forming ametallic salt with the Hyex rosin acid. Thus, the Hyex rosin acid may be reacted with an alkali metal hydroxide, for example, sodium or potassium hydroxide, to produce the corresponding alkali metal salt of the Hyex rosin or with a heavy metal oxide or hydroxide, as for example, lead, cobalt, or manganese hydroxide, to produce the corresponding heavy metal salts.

The product in accordance with this invention,

is a compound which contains somewhere in its plc, be of one of the following types: carboxylic acid, ester, alcohol, ether, hydrocarbon, metallic salt, etc. These compounds will be found to resemble, in general physical appearance, the compounds which have not been treated by the method in accordance with this invention, although frequently they are lighter in color and have a higher melting point than the corresponding untreated product. Chemically the treated and untreated compounds are identical with respect to the functional group, but difierent in regard to their chemical unsaturation.

Due to the substantially saturated character of the products prepared in accordance with this invention, their use will be found to be highly advantageous in many. products in which untreated Rosinyl compounds are now used. Thus, Hyex-grosin, Hyex rosin acids, Hyex rosin as high boiling solvents for gums and resins, and as ingredients in greases. The alkali metal salts of the Hyex rosins are useful as paper size and soaps, and are advantageous in this use due to their resistance to chemical oxidation and as intermediates for additional syntheses. The heavy metal salts of Hyex rosin, such as, for example, those containing manganese, cobalt, zinc,- lead, etc.,- are particularly useful as driers in paints and varnishes, since solutions containing such driers' remain bright and of constant drying strength on aging.

The carboxylic acids included within the scope of this invention are the isomeric rosin acids, or commercial mixtures thereof in the various types of rosins, mentioned hereinbefore, which have been subjected to the Hyex treatment. The esters, in .accordance with this invention, are .compounds having the following formula:

R-COO-A in which R is a hydrocarbon nucleus of one of the isomeric rosin acids, which has been subjected to the Hyex treatment either before, during, or after the esterification reaction and A is a group derived from an alcohol. The ethers, in accordance with this invention, are compounds having the following 'formula: R-'-CH2-0-A v in which the R and A have the same meaning as in the formula given for the esters. The hydrocarbons, in accordance with this invention are the hydrocarbon nuclei of the isomeric rosin acids which have been subjected to the Hyex treatment and from which the carboxyl group has been removed. Such Hyex Rosinyr' hydro-' carbons may be produced by subjecting rosin or a rosin acid to the Hyex treatment and then treating the resulting Hyex rosin or Hyex rosin acid to'remove the carboxyl group. Alternately the rosin or rosin acid may be decarboxylated, by treatment with a sulfonic acid catalyst or any other reagent known to produce the decarboxylation of rosin, and the 'resulting hydrocarbon then subjected to the Hyex treatment. The salts, vin accordance with this invention, are metal salts of a Hyex rosin or Hyex rosin acid. Such salts will desirably be produced by subjecting the rosin or rosin acid to the Hyex treatment and then forming the salt by reaction with a suitable metal compound, such as, for example, the metal hydroxide. Alternately, but less desirable, the rosin or rosin acid may be treated with a suitable metal compound to form the salt, and this salt then subjected to the Hyex treatment.

The following table shows comparative values of various chemical constants for rosin which The decrease in thiocyanate number and in oxygen absorption exhibited by the treated 1 wood rosin is proof of the marked decrease in chemical unsaturation produced by treatment in accordance with this invention. The fact that the saponification number is practically the same for both the treated and untreated rosins'demonstrates that the carboxyl groups of the rosin acids have been unchanged by the treatment,

which must therefore affect the hydrocarbon nucleus only.

The following table shows comparative values a of various chemical constants for a treated, to-

gether with those of the corresponding untreated,

rosin acid.

TABLE II Abietic acid Hyex abietic (before treatment) acid Thiocyanate -No. 15-55; Melting point l(i0l65 G. Color (when melted) Pale straw Practically color- 'less. Oxygen absorption (percent 55% None. of total absorbed by two double bonds).

. Here, as in'the case of I rosin, the lowered thiocyanate number and oxygen "absorption treated abietic acid.

EXAMPLE I Preparation of Hyex rosins and Hyexzrosin acids Samples of French gum rosin, dihydroabietic' acid saturation), recrystallized dihydroabietic acid (50% saturation),."FF grade wood rosin, and G grade American gumrosin, r e-- spectively, were contacted with a catalyst of palladium supported on alumina, which was pre pared as described hereinbefore, for a period of properties of the treated and untreated samples given in the following table:

has been subjected to the Hyex reaction together TABLE III with those of the corresponding untreated rosin. Analyses of Hyex rosins Thiocyanate No. 2 255??? Specific rotation Rosin treated V i? Treated i? Treated i?" Treated c'. 0. Y French gum rosin. 100 24 92 99 .9 Dihgczgooqabiegie 4 +15 aci sa 0 5 77 87 pin awibie ic 21 4 3 5 ac: recryst. 89 43.2 "FF" wood rosin" 99 i 86 83 "j. Bi G American gum rosin -94 8 95 demonstrates the saturated character of the 4 These data demonstrate that the treatment of each of the rosins and rosin acids listed, by the process inaecordance with this invention, makes substantial reduction in their unsaturation, as shown by the decrease in the thiocyanate number, and substantially increases the melting point..-

EXAMPLE I: Preparation of Hyex wood rosin in solution A mixture of 25 parts by weight of "1? wood rosin, 10 parts by weight of the palladium catalyst supported on grahular alumina described hereinbefore, and '25 parts by weight of decane was placed in a bomb and heated to a temperature of 235 C- and a pressure of "75 lbs. per sq. in.

for one hour. At the end of this period, the.

product was filtered and the treated-rosin recovered from the decane solution by evaporating the decane under atmospheric and finally under Acid number reduced pressure. Comparative analyses of this product and of the original "I" wood rosin are given in Table IV.

TABIlE IV "I' wood rosin (untreatod) T t d III wood rosin Thiocyanate value 93 The data given in the above table demonstrate American gum rosin similar in properties to that described in,,Table m, by following the same procedure given in Example III for the preparation of the crude Hyex wood rosin oil. From 400 g. of the Hyex gum rosin there was, obtained 375 g. of a crude rosin oil which gave the following analyses: Y

Acid number ..Q -9.0 Refractive index at 20 C 1.6543 Thiocyanate value- 31.5

stantially neutral Hyex American gum rosin oil/20 which gave the following analyses:

that the treatment of a solution of 1 wood rosin in decane, in accordance with this invention, produces a, marked decrease in the unsaturation of the I wood'rosin, as measured by the thiocyanate value, with a relatively unimportant decrease in acidity, as measured by the acid number. I

- EXAMPLE m Preparation of Hyex wood rosin oil r Four hundred g. of the Hyex wood rosin de-' scribed in Table I was heated to 285 C. with 8 of 1% by weight of paratoluene sulfonic acid.

, The temperature was then raised to 320 6., and.

maintained at this point for 4- hours. This treat- ..ment produced 390 g. of a crude rosin oil having an acid number of 58 as compared with an acid number of160 for the original Hyex wood rosin. Substantally neutral oil was then produced by dissolving 150 g. of this crude oil in 200 got i petroleum ether, washing this solution with an aqueous caustic soda solution, and evaporating V the'petroleum ether. Niuety-seveng. of an oil I Refractive index at 20 i3 --I-- Thiocyanate value 40.5

having the following analyses was obtained:

Acid number 1.0

A second portion of the crude rosin oil was puri- Fifteen g. of sodium carbonate and 25 g. of water were added to 150' g. of .the crude oil. Whenthe reaction was complete the mixture was heated and the water evaporated. This product was then distilled under reduced, pressure to give 80 g. of a pale rosin oil as a distillate. This pal rosi oil gave the following analyses:

Acid number; l 0.75 Refractive index at 20 C; 1.5543

Thiocyanate value--- 31.5

t Preparation of Hyex gum rosin. oil

Crude rosin oil was prepared from a Hyex Acid number 1.5 Refractive index at -20 C 1.5587 Thiocyanate value-.. 28

Acid number 1.0, I Refractive index at 20 C 1.5517 Thiocyanate value"; 28.0

It will be understood that the details and examples hereinbefore set forth are illustrative only,

and that the invention as herein broadly de-- scribed and claimed is in no way limited-thereby.

It will be understood that the term unsaturation is used in this specification and in the appended claims torefer to the unsatisfied carbon valences of the type represented by a double bond in unsaturated aliphatic compounds and conveniently measured by the thiocyanate value.

This application isa division of my application for- United States Letters Patent, Serial No. 84,877, filed June 12, 1936, which is in turn a continuation-in-part of my application for "United States Letters Patent, Serial No. 6,403, filed February 13, 1935.

What I claim and desire to protect by Letters Patent is: a v

1. Themethod of treating a hydrocarbon deerived by decarboxylation of a material from the group consisting of rosin, partially hydrogenated rosin, rosin acids, and partially hydrogenated rosin acids which includes contacting the hydrocarbon in the liquid phase with an active hydrogenation catalyst under conditions of reaction adapted to produce an intraand inter-molecular rearrangementofhydrdgen atoms in the hydrocarbon and in the absence of added substances capable of reducing the unsaturation of the hydrocarbon. a

2. The method of treating a hydrocarbon derived by decarboxylation of a material from the group consisting of rosin, partially hydrogenated rosin, rosin acids, and partially hydrogenated rosin acids which includes heating the hydrocarbon in the liquid phase with an active hydrogenation catalyst mnder conditions of reaction adapted to produce an intra-and inter-molecular rearrangement of hydrogen atoms in the hydrocarbon and in the absence of added substances capable of reducing the unsaturation of the hydrocarbon.

3. The method of treating a hydrocarbon derived by decarboxylation of a material from the group consisting of rosin, partially hydrogenated rosin, rosin acids, and partially hydrogenated rosin acids which includes heating the hydrocarbon with an active hydrogenation catalyst at a temperature of from about 150 C. to about 250 C. in theabsence oiadded substances capable of reducing the unsaturation oi the hydrocarbon.

4. The method of treating a hydrocarbon derived by decarboxylation of a material from the group consisting of rosin, partially hydrogenated rosin, rosin acids, and partially hydrogenated rosin acids which includes contacting the hydro-' carbon in the liquid phase with a noble metal hydrogenation catalyst under conditions of reaction adapted to produce an intraand inter-' molecular rearrangement of hydrogen atoms in the hydrocarbonand in the absence of added substances capable of reducing the unsaturation oi the hydrocarbon.

5. The method or treating a hydrocarbon derived by decarboxylation of a material from the group consisting of rosin, partially hydrogenated rosin,. rosin l acids, and partially hydrogenated rosin acids which includes contacting the hydrocarbon in the liquid phase with a base metal catalyst under conditions of reaction adapted to produce an intraand intermolecular rearrangement of hydrogen atoms in the hydrocarbon and in the absence 01' added substances capable of reducing the unsaturation of the hydrocarbon.

6. The method ottreating a hydrocarbon derived by 'recarboxylation of a material from the group consisting oi rosin, partially hydrogenated rosin, rosin acids, and partially hydrogenated rosin acids which includes contacting the hydro carbon in the liquid phase with a palladium cataly'st under conditions oi reaction adapted to produce an intraand inter-molecular-rearrangement of hydrogen atoms in thehydrocarbonand in the absence or added substances capable of reduclng the unsaturation oi the hydrocarbon.

'7. The method of treating a hydrocarbon derived by decarboxylation of a material from thegroup consisting of rosin. partially-hydrogenated rosin, roan acids, and partially hydrogenated rosin acids which includes contacting the hydrocarbon in the liquid phase with a catalyst' comprising palladium black supported on gunent unsaturation as compared with French gum armsso ailar alumina under conditions of reaction adapted to produce an intraand inter-molecular rearrangement of hydrogen atoms in the hydrocarbon and in the absence of added substances capable of reducing the unsaturation oi the hydrocarbon.

8.'The method of treating a hydrocarbon derived by. decarboxylation of a material from the group consisting of rosin, partially hydrogenatedrosin, rosin acids, and partially hydrogenated rosin acids which includes contacting the hydrocarbon in the liquid phase with an active hydrogenation catalyst at a temperature within the range 01' from about 220 C. to about 250 C. in. the absence or added substances capable of reducing the unsaturation of the hydrocarbon.

9. As a newcomposition of matter, a liquid rearrangement product of rosin oil, said product g-substantially the same empirical formula as rosin oil and characterized bya subreduction in apparent unsaturationas compared with rosin oil, said product having a thiocyanate value not in excess of about 41. y,

10. As a new composition or matter, a liquid rearrangement product or wood rosin oil, said product possessing substantially the same empirical formula as wood rosin oil by a substantial resistance to oxidation and a substantial reduction in apparent unsaturation as compared with wood rosin. oil, said product having .a thiocyanate value not inexce'ss of about 41. i a

11. As a new composition oiv matter, a liquid rearrangement product of French gum rosin 011, said product possessing substantially the same empirical formula as French gum rosin oil and characterized by a substantial resistance to oxidationand a substantial reduction in apparrosin oil, said product having a thiocyanate value not in excess oLabout 41.

12. As a new composition of matter, a liquid rearrangement product of American gum rosin oil said product possessing substantially the same empirical i'ormula as American gum rosin oil and characterized by a substantial resistance to oxidation and a substantial reduction in apparent. unsaturation as compared with American' a thiocyanate 50 gum rosin oilgsaid product having value not in excess or about 41. V

nnwmmnrrruaim.

' stantial resistance to oxidation and a substantial 

